[go: up one dir, main page]

EP1301652B1 - Improving effectiveness of artificial hip by gcib - Google Patents

Improving effectiveness of artificial hip by gcib Download PDF

Info

Publication number
EP1301652B1
EP1301652B1 EP01952533.6A EP01952533A EP1301652B1 EP 1301652 B1 EP1301652 B1 EP 1301652B1 EP 01952533 A EP01952533 A EP 01952533A EP 1301652 B1 EP1301652 B1 EP 1301652B1
Authority
EP
European Patent Office
Prior art keywords
gas
surgical implant
ion beam
clusters
inert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01952533.6A
Other languages
German (de)
French (fr)
Other versions
EP1301652A4 (en
EP1301652A1 (en
Inventor
Allen R. c/o Exogenesis Corporation KIRKPATRICK
Vincent c/o Exogenesis Corporation DIFILIPPO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Exogenesis Corp
Original Assignee
Exogenesis Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exogenesis Corp filed Critical Exogenesis Corp
Publication of EP1301652A1 publication Critical patent/EP1301652A1/en
Publication of EP1301652A4 publication Critical patent/EP1301652A4/en
Application granted granted Critical
Publication of EP1301652B1 publication Critical patent/EP1301652B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F4/00Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48Ion implantation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/50Substrate holders
    • C23C14/505Substrate holders for rotation of the substrates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/30Electron-beam or ion-beam tubes for localised treatment of objects
    • H01J37/317Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/3094Designing or manufacturing processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/34Acetabular cups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2002/30001Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
    • A61F2002/30667Features concerning an interaction with the environment or a particular use of the prosthesis
    • A61F2002/30682Means for preventing migration of particles released by the joint, e.g. wear debris or cement particles
    • A61F2002/30685Means for reducing or preventing the generation of wear particulates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2002/30934Special articulating surfaces
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/36Femoral heads ; Femoral endoprostheses
    • A61F2/3609Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/3611Heads or epiphyseal parts of femur
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00011Metals or alloys
    • A61F2310/00029Cobalt-based alloys, e.g. Co-Cr alloys or Vitallium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/06Sources
    • H01J2237/08Ion sources
    • H01J2237/0812Ionized cluster beam [ICB] sources
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32Processing objects by plasma generation
    • H01J2237/33Processing objects by plasma generation characterised by the type of processing
    • H01J2237/336Changing physical properties of treated surfaces

Definitions

  • This invention relates generally to medical devices or surgical implants such as artificial hip joints and, more particularly to a method and system for smoothing surgical implants such as artificial hip joints using gas cluster ion beam technology.
  • Total hip replacement or arthroplasty
  • arthroplasty is a surgical procedure in which the diseased parts of a hip joint are removed and replaced with new, artificial parts.
  • these artificial hip joint components are being produced from improved bearing materials such as highly cross-linked polyethylene, metal-on-metal, and ceramic-on-ceramic implants.
  • osteolysis is a major problem and is believed to be due to an inflammatory process brought on by particulate matter or debris dislodged from the implants themselves. Some degree of osteolysis is present in up to 40% of all cases within 10 years of surgery.
  • the problem is articulating surfaces between the femoral and acetabular components of the implant produce wear debris which is an important contributor to pathologic tissue response. Therefore, the long-term threat to component failure from a biologic standpoint is this wearing debris associated with osteolysis.
  • the critical initiating sequence involves the interaction between small particulate materials and responding specialized cells. The number, size, distribution, and type of particulate material are also believed to have an affect on the process.
  • the material causing the most tissue reaction appears to be the particulate polyethylene with particle sizes of approximately 0.5 micron.
  • Metallic debris also causes tissue reaction with significant quantities identified with particle sizes somewhat larger than the polyethylene debris. The major effect of this larger metallic debris may relate to promoting wear of the polyethylene, with the derivative polyethylene particles of submicron size triggering the cellular response.
  • smaller metal particles and ions have been demonstrated to be active in direct stimulation of biologic processes as well.
  • United States Patent Specification no US-A- 4 968 006 discloses a method and an apparatus for the ion implantation of spherical surfaces.
  • the method includes the provision of a revised fixture by which a plurality of spherical workpieces is presented to a large area ion beam in a way that entire respective spherical surfaces are uniformly ion implanted to improve their surface characteristics.
  • the fixture includes a disc mounted for motion about two axes normal to each other, a plurality of holes formed in a the disc loosely to accommodate therein a plurality of spherical workpieces, each of the plurality of holes formed with a spherical bottom and having a cleaning orifice, cooling means disposed on one side of the disc, a thermocouple operatively mounted in association with the disc, and a cover plate mounted on a second side of the disc and provided with a plurality of apertures concentric with the plurality of holes formed in the disc.
  • the method includes randomization of the motion about one of the two axes of motion by interrupting this motion for about 15 to about 30 seconds once every 90 to about 120 seconds.
  • United States Patent Specification no US-A- 5 123 924 discloses a surgical implant, formed of cobalt-chromium and its alloys in contact with a bearing surface formed by ultra-high molecular weight polyethylene (UHMWPE), and a process of its manufacture.
  • the improved surgical implant is designed to reduce the wear of the UHMWPE component of the surgical implant, enhancing its useful life.
  • the process essentially includes the ion implantation of the cobalt-chromium component, with a resultant increase in its microhardness and a decrease in its coefficient of friction, particularly when articulating against the UHMWPE component.
  • United States Patent Specification no US-A- 5 133 757 discloses a load-bearing plastic orthopaedic joint implant, formed at least partially of UHMWPE or high density polyethylene material, and a process of subjecting at least the load-bearing surface thereof to ion implantation so as to improve its surface characteristics.
  • Such surface characteristics result, inter alia , from the formation in the treated surfaces, of increased carbon to carbon bonds, diamond-like carbon chain scissions and wherein the implanted ions do not form precipitate chemical compounds with the plastic material.
  • United States Patent Specification no US-A- 5 980 974 discloses an improved coated orthopaedic implant component.
  • the implant may be coated with platinum, iridium or other metals for improved characteristics.
  • Ion beam coating orthopaedic parts by ion implanting the parts with zirconium ions while the parts are immersed in an oxygen-containing background gas is also disclosed.
  • the adhesion of the graded interface zirconium oxide surface layer so formed is assisted by the initial removal of surface contamination using an ion bombardment and the deposition of an intermediate layer of platinum or similar metal or silicon between the orthopaedic metal component and the zirconium oxide.
  • United States Patent Specification no US-A-5 459 326 discloses a method of treating the surface of a substrate using an extra-low-speed ion beam.
  • the method involves forming a cluster, which is a lump-shaped group of atoms or molecules of a gaseous substance at the ambient temperature, by adiabatic expansion form a high pressure region into a high-vacuum region thorough a small-bore conical nozzle, pouring electrons onto the cluster, accelerating the thus generated cluster ions by acceleration voltage, and irradiating the ions onto the surface of a solid.
  • the method permits surface cleaning of a substrate without causing damage or defects, ion injection into the very shallow surface layer portion, and CVD.
  • the present invention applies gas cluster ion beam (GCIB) technology in order to modify the component's surface, thereby substantially reducing wear debris and osteolysis complications.
  • GCIB gas cluster ion beam
  • the approach of the surface modification comprises an atomic level surface smoothing utilizing GCIB to super smooth the femoral heads and/or the surfaces of the acetabular cups to reduce frictional wear at the interface of the bearing surfaces.
  • a reduction in polyethylene debris and metal debris by GCIB smoothing on one or both bearing surfaces of a total hip prosthesis reduces osteolysis, results in a substantial cost savings to the healthcare system, and reduces patient pain and suffering.
  • Gas cluster ions are formed from large numbers of weakly bound atoms or molecules sharing common electrical charges and accelerated together through high voltages to have high total energies. Cluster ions disintegrate upon impact and the total energy of the cluster is shared among the constituent atoms. Because of this energy sharing, the atoms are individually much less energetic than the case of conventional ions or ions not clustered together and, as a result, the atoms penetrate to much shorter depths. Surface sputtering effects are orders of magnitude stronger than corresponding effects produced by conventional ions, thereby making important microscale surface smoothing effects possible that are not possible in any other way.
  • Patent 5,459,326 that such individual atoms are not energetic enough to significantly penetrate a surface to cause the residual sub-surface damage typically associated with plasma polishing. Nevertheless, the clusters themselves are sufficiently energetic (some thousands of electron volts) to effectively etch, smooth, or clean hard surfaces.
  • the energies of individual atoms within a gas cluster ion are very small, typically a few eV, the atoms penetrate through only a few atomic layers, at most, of a target surface during impact.
  • This shallow penetration of the impacting atoms means all of the energy carried by the entire cluster ion is consequently dissipated in an extremely small volume in the top surface layer during a period on the order of 10 -12 seconds.
  • the deposited energy density at the impact site is far greater than in the case of bombardment by conventional ions.
  • FIG. 1 of the drawings shows the gas cluster ion beam (GCIB) processor 100 of this invention utilized for the surface smoothing of a surgical implant such as an artificial hip joint component 10.
  • the processor 100 is made up of a vacuum vessel 102 which is divided into three communicating chambers, a source chamber 104, an ionization/acceleration chamber 106, and a processing chamber 108 which includes therein a uniquely designed workpiece holder 150 capable of positioning the artificial hip joint for uniform smoothing by a gas cluster ion beam.
  • the three chambers are evacuated to suitable operating pressures by vacuum pumping systems 146a, 146b, and 146c, respectively.
  • a condensable source gas 112 (for example argon, nitrogen, oxygen, or a gas mixture) stored in a cylinder 111 is admitted under pressure through gas metering valve 113 and gas feed tube 114 into stagnation chamber 116 and is ejected into the substantially lower pressure vacuum through a properly shaped nozzle 110, resulting in a supersonic gas jet 118. Cooling, which results from the expansion in the jet, causes a portion of the gas jet 118 to condense into clusters, each consisting of from several to several thousand weakly bound atoms or molecules.
  • a gas skimmer aperture 120 partially separates the gas molecules that have not condensed into a cluster jet from the cluster jet so as to minimize pressure in the downstream regions where such higher pressures would be detrimental (e.g., ionizer 122, high voltage electrodes 126, and process chamber 108).
  • Suitable condensable source gases 112 include, but are not necessarily limited to argon, nitrogen, carbon dioxide, oxygen and mixtures of these gases.
  • the ionizer 122 is typically an electron impact ionizer that produces thermoelectrons from one or more incandescent filaments 124 and accelerates and directs the electrons causing them to collide with the gas clusters in the gas jet 118, where the jet passes through the ionizer 122.
  • the electron impact ejects electrons from the clusters, causing a portion the clusters to become positively ionized.
  • a set of suitably biased high voltage electrodes 126 extracts the cluster ions from the ionizer 122, forming a beam, then accelerates the cluster ions to a desired energy (typically from 1 keV to several tens of keV) and focuses them to form a GCIB 128 having an initial trajectory 154.
  • Filament power supply 136 provides voltage V F to heat the ionizer filament 124.
  • Anode power supply 134 provides voltage V A to accelerate thermoelectrons emitted from filament 124 to cause them to bombard the cluster containing gas jet 118 to produce ions.
  • Extraction power supply 138 provides voltage V E to bias a high voltage electrode to extract ions from the ionizing region of ionizer 122 and to form a GCIB 128.
  • Accelerator power supply 140 provides voltage V Acc to bias a high voltage electrode with respect to the ionizer 122 so as to result in a total GCIB acceleration energy equal to V Acc electron volts (eV).
  • One or more lens power supplies (142 and 144, for example) may be provided to bias high voltage electrodes with potentials (V L1 and V L2 for example) to focus the GCIB 128.
  • a medical device such as an artificial hip joint component 10 (shown in Figure 1 as an acetabular cup, or replaced by a femoral head) to be processed by the GCIB processor 100 is held on a workpiece holder 150, disposed in the path of the GCIB 128 (148).
  • the workpiece holder 150 is designed in a manner set forth below to appropriately manipulate the hip joint component 10.
  • the artificial hip joint surfaces that are non-planar that is may be of a sphere-like or cup-like configuration, preferably remain oriented within a specific angle tolerance with respect to the normal beam incidence to obtain optimal smoothing of the hip joint surfaces utilizing GCIB. It has been determined that optimum smoothing occurs when the GCIB strikes the workpiece at near-normal incidence (for example within +/- 15 degrees of normal), but it has also been shown that incident angles deviating up to about 45° from normal can produce effective smoothing. Additionally in the case of a cup-like joint component, it is necessary that appropriate portions of the interior surface of the cup be processed despite the fact that the rim of the cup may shadow portions of the interior surface in certain orientations.
  • hip joint fixture or workpiece holder 150 with the ability to be fully articulated to orient all non-planar surfaces to be modified within that angle tolerance at a constant exposure level for process optimization and uniformity. More specifically, when smoothing an artificial hip joint component 10, the workpiece holder 150 is rotated and articulated by a mechanism 152 located at the end of the GCIB processor 100.
  • the articulation/rotation mechanism 152 preferably permits 360 degrees of device rotation about longitudinal axis 154 and sufficient device articulation about an axis 156 perpendicular to axis 154 to preferably maintain the artificial hip joint surface to within +/- 15 degrees from normal beam incidence.
  • a scanning system may be desirable to produce uniform smoothness.
  • two pairs of orthogonally oriented electrostatic scan plates 130 and 132 may be utilized to produce a raster or other scanning pattern over an extended processing area.
  • a scan generator 156 provides X-axis and Y-axis scanning signal voltages to the pairs of scan plates 130 and 132 through lead pairs 158 and 160 respectively.
  • the scanning signal voltages are commonly triangular waves of different frequencies that cause the GCIB 128 to be converted into a scanned GCIB 148, which scans the entire surface of the hip joint component 10.
  • electrostatic scanning of the GCIB 128 across the workpiece is illustrated, it is also possible (not shown) to achieve similar results by holding the GCIB 128 stationary and mechanically scanning the workpiece through the beam to achieve processing of large workpieces.
  • the diameter of the beam at the workpiece's surface can be set by selecting the voltages (V L1 and/or V L2 ) of one or more lens power supplies (142 and 144 shown for example) to provide the desired beam diameter at the workpiece.
  • FIG 3 shows an alternate embodiment gas cluster ion beam processing system 200 of the present invention, similar to the gas cluster ion beam processing system 100 of Figure 1 , but having been configured somewhat differently for GCIB processing of sphere-like workpiece 20, for example the ball portion of a hip joint prostheses for surgical implantation.
  • a scanned GCIB 148 is directed toward the sphere-like workpiece 20 disposed in the path of the scanned GCIB 148 in such a way that it intercepts a portion of the scanned GCIB 148.
  • the portion of the scanned GCIB which is not intercepted by the workpiece 20 continues and strikes ion beam current collector 212, which collects electrical current due to the ions in the portion of scanned GCIB 148 that strikes the collector 212.
  • the scanned GCIB 148 scans across a predetermined area on the surface of the current collector 212, the area including the area shadowed by the workpiece 20.
  • the ion current collected by the charge collector 212 flows through electrical lead 214 into current integrator/processor 218, which integrates the collected current and, by taking into account the predetermined fraction of the scanned beam that is intercepted by the workpiece, calculates and displays the total dose, in ions/cm2, that would irradiate the workpiece if it were a flat surface perpendicular to the beam axis 220 and having a circular radius equal to the radius of the sphere-like workpiece 20.
  • Workpiece 20 typically has a opening, which may be tapered, that may be used to attach it to the end of a shaft 204 and it is supported and disposed in the beam path by the shaft 204.
  • the shaft 204 passes through rotary motion vacuum feedthrough 208 in an access plate 216 of the processing chamber 108.
  • a conventional rotary motor 210 rotates shaft 204 and attached workpiece 20 during irradiation of the workpiece 20 by the scanned GCIB 148.
  • the motor speed is chosen to provide a rotation period that is short compared to the processing time so that the GCIB dose is deployed circumferentially uniformly about the processed portion of the sphere-like workpiece 20.
  • Rotary shaft 204 is disposed so that its axis of rotation is at an angle 206 to the axis 220 of scanned GCIB 148.
  • the dose applied must be indicated by the current integrator/processor 218 to be larger than the desired dose by the factor of the Area ratio given in Eqn. 1. This assures that the average dose received by the sphere-like workpiece is equal to the desired dose, but the dose is not uniform across the surface of the sphere-like workpiece 20. If greater uniformity of dose is desired on the sphere-like workpiece or if it is desired to achieve a more limited range of GCIB incident angle on the workpiece, a more complex positioning mechanism capable of rotating the sphere about two axes can be used, like that shown in Figure 2 .
  • a hip component 10 surface composed of a cobalt-chrome alloy had gross surface micro-roughness before GCIB treatment.
  • the surface roughness measured an average roughness (R a ) of 3.86 angstroms and a root-mean-square roughness (R RMS ) of 5.28 angstroms. These irregularities highlight the surface micro-roughness problem at the cellular level where osteolysis begins.
  • a hip joint component 10 surface composed of cobalt-chrome alloy after argon GCIB processing showed the surface micro-roughness has been reduced without any measurable physical or structural change to the integrity of the prosthesis itself.
  • the post-GCIB surface roughness measured an R a of 2.62 angstroms and an R RMS of 3.34 angstroms.
  • Effective argon gas cluster ion beam doses, using beam energies of from about 2 to about 50 keV, for smoothing cobalt-chrome alloy surfaces are typically in the range of from about 1 X 10 15 ions/cm 2 to about 1 X 10 17 ions/cm 2 and can be determined experimentally for other materials.
  • FIG 4 shows an AFM image of a surface of a hip joint component 20 made from an ASTM F1537 wrought Cobalt-Chrome-Molybdenum (Co-Cr-Mo) alloy prepared and polished conventionally.
  • the AFM-measured R a of this surface is 21.1 angstroms. It was learned that processing this surface with an argon GCIB failed to produce satisfactory reduction in the R a of the surface, even with extended processing doses.
  • the AFM image, shown in Figure 4 of the surface prior to GCIB processing is quite rough, with large numbers of elevated regions (asperities).
  • the asperities are seen to fall into two size ranges when viewed on the scale of the AFM image, "small” and “larger".
  • Experimentation revealed that the small asperities and other high spacial frequency roughness features were readily removed by GCIB processing using inert argon gas clusters.
  • the size distribution of the asperities is clearly enough demarcated that it is believed the two sizes may arise from different phenomena.
  • the "small” asperities have a linear streaked surface distribution that suggests that they may be some kind of residue or result of the conventional mechanical polishing process. While the "small” asperities are sometimes organized in a linear streak pattern, the "larger” ones appear randomly oriented, generally fewer in number, and somewhat platelet-like in shape.
  • the reactive GCIB processing preferentially etches the "larger” asperities, which may be of the form of micro-grains of metal of a different phase than the matrix. This leaves a micro-pit where the "larger" asperities previously stood above the surface. Subsequent additional inert argon GCIB processing removes any sharp transitions that may otherwise remain near the pits.
  • Figure 5 shows an AFM image of a surface of a hip joint component 20 composed of an ASTM F1537 wrought Cobalt-Chrome-Molybdenum (Co-Cr-Mo) alloy from the same starting sample as that of Figure 4 , but processed using a two step GCIB process according to an embodiment of the present invention.
  • the surface is exposed to a dose of approximately 3 X 10 16 cluster ions/cm 2 of clusters formed from a reactive gas, 50% argon mixed with 50% oxygen.
  • the surface is exposed to approximately 3 X 10 16 cluster ions/cm 2 of clusters formed from the inert gas, argon.
  • the average roughness R a of this surface as measured by AFM is 15.2 angstroms, notably reduced from the 21.1 R a of the starting material previously shown in Figure 4 , with much of the residual roughness due to the presence of the micro-pits. Furthermore, the nature of the surface is transformed from a surface with elevated asperities, conducive wear and conducive to inducing wear in mating surfaces, to a largely smooth upper surface with scattered smooth micro-pits. The increased smoothness of the upper surface and the greater bearing surface is a significantly superior surface for reduced wear and particle generation in surgically implanted prostheses. Comparison of Figures 4 and 5 shows the dramatic surface improvement obtained by applying both reactive and inert GCIB processing to this hip joint component.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Transplantation (AREA)
  • Vascular Medicine (AREA)
  • Cardiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Prostheses (AREA)
  • Physical Vapour Deposition (AREA)
  • Materials For Medical Uses (AREA)

Description

    FIELD OF THE INVENTION
  • This invention relates generally to medical devices or surgical implants such as artificial hip joints and, more particularly to a method and system for smoothing surgical implants such as artificial hip joints using gas cluster ion beam technology.
  • BACKGROUND OF THE INVENTION
  • Total hip replacement, or arthroplasty, is a surgical procedure in which the diseased parts of a hip joint are removed and replaced with new, artificial parts. Presently, these artificial hip joint components are being produced from improved bearing materials such as highly cross-linked polyethylene, metal-on-metal, and ceramic-on-ceramic implants. After the hip replacement, osteolysis is a major problem and is believed to be due to an inflammatory process brought on by particulate matter or debris dislodged from the implants themselves. Some degree of osteolysis is present in up to 40% of all cases within 10 years of surgery.
  • The problem is articulating surfaces between the femoral and acetabular components of the implant produce wear debris which is an important contributor to pathologic tissue response. Therefore, the long-term threat to component failure from a biologic standpoint is this wearing debris associated with osteolysis. The critical initiating sequence involves the interaction between small particulate materials and responding specialized cells. The number, size, distribution, and type of particulate material are also believed to have an affect on the process.
  • Quantitatively, the material causing the most tissue reaction appears to be the particulate polyethylene with particle sizes of approximately 0.5 micron. Metallic debris also causes tissue reaction with significant quantities identified with particle sizes somewhat larger than the polyethylene debris. The major effect of this larger metallic debris may relate to promoting wear of the polyethylene, with the derivative polyethylene particles of submicron size triggering the cellular response. However, smaller metal particles and ions have been demonstrated to be active in direct stimulation of biologic processes as well.
  • United States Patent Specification no US-A- 4 968 006 discloses a method and an apparatus for the ion implantation of spherical surfaces. The method includes the provision of a revised fixture by which a plurality of spherical workpieces is presented to a large area ion beam in a way that entire respective spherical surfaces are uniformly ion implanted to improve their surface characteristics. The fixture includes a disc mounted for motion about two axes normal to each other, a plurality of holes formed in a the disc loosely to accommodate therein a plurality of spherical workpieces, each of the plurality of holes formed with a spherical bottom and having a cleaning orifice, cooling means disposed on one side of the disc, a thermocouple operatively mounted in association with the disc, and a cover plate mounted on a second side of the disc and provided with a plurality of apertures concentric with the plurality of holes formed in the disc. The method includes randomization of the motion about one of the two axes of motion by interrupting this motion for about 15 to about 30 seconds once every 90 to about 120 seconds.
  • United States Patent Specification no US-A- 5 123 924 discloses a surgical implant, formed of cobalt-chromium and its alloys in contact with a bearing surface formed by ultra-high molecular weight polyethylene (UHMWPE), and a process of its manufacture. The improved surgical implant is designed to reduce the wear of the UHMWPE component of the surgical implant, enhancing its useful life. The process essentially includes the ion implantation of the cobalt-chromium component, with a resultant increase in its microhardness and a decrease in its coefficient of friction, particularly when articulating against the UHMWPE component.
  • United States Patent Specification no US-A- 5 133 757 discloses a load-bearing plastic orthopaedic joint implant, formed at least partially of UHMWPE or high density polyethylene material, and a process of subjecting at least the load-bearing surface thereof to ion implantation so as to improve its surface characteristics. Such surface characteristics result, inter alia, from the formation in the treated surfaces, of increased carbon to carbon bonds, diamond-like carbon chain scissions and wherein the implanted ions do not form precipitate chemical compounds with the plastic material.
  • United States Patent Specification no US-A- 5 980 974 discloses an improved coated orthopaedic implant component. The implant may be coated with platinum, iridium or other metals for improved characteristics. Ion beam coating orthopaedic parts by ion implanting the parts with zirconium ions while the parts are immersed in an oxygen-containing background gas is also disclosed. The adhesion of the graded interface zirconium oxide surface layer so formed is assisted by the initial removal of surface contamination using an ion bombardment and the deposition of an intermediate layer of platinum or similar metal or silicon between the orthopaedic metal component and the zirconium oxide.
  • United States Patent Specification no US-A-5 459 326 discloses a method of treating the surface of a substrate using an extra-low-speed ion beam. The method involves forming a cluster, which is a lump-shaped group of atoms or molecules of a gaseous substance at the ambient temperature, by adiabatic expansion form a high pressure region into a high-vacuum region thorough a small-bore conical nozzle, pouring electrons onto the cluster, accelerating the thus generated cluster ions by acceleration voltage, and irradiating the ions onto the surface of a solid. The method permits surface cleaning of a substrate without causing damage or defects, ion injection into the very shallow surface layer portion, and CVD.
  • It is therefore an object of this invention to provide an atomic level surface smoothing of artificial hip joints. It is a further object of this invention to provide surface modification of artificial hip joints by gas cluster ion beams to alleviate the problems associated with osteolysis.
  • SUMMARY OF THE INVENTION.
  • According to an aspect of the present invention, there is provided a method for smoothing the surface materials of a surgical implant as specified in claim 1. According to another aspect of the present invention, there is provided a polished surgical implant component as specified in claim 9.
  • The objects set forth above as well as further and other objects and advantages of the present invention are achieved by the invention described hereinbelow.
  • Several factors have been suggested to minimize the production of wear debris: (1) femoral heads with highly polished cobalt alloy or polished ceramics are believed to be advantageous in minimizing effects of wear on the polyethylene surfaces of the acetabular cups; (2) new highly cross-linked polyethylene acetabular cups are gaining some increased surgical use as a means of decreasing wear and; (3) hard-on-hard implants such as metal-on-metal and ceramic-on-ceramic implants are expected to reduce wear debris.
  • Regardless of the materials used in the artificial hip joint designs, the present invention applies gas cluster ion beam (GCIB) technology in order to modify the component's surface, thereby substantially reducing wear debris and osteolysis complications. The approach of the surface modification comprises an atomic level surface smoothing utilizing GCIB to super smooth the femoral heads and/or the surfaces of the acetabular cups to reduce frictional wear at the interface of the bearing surfaces.
  • A reduction in polyethylene debris and metal debris by GCIB smoothing on one or both bearing surfaces of a total hip prosthesis reduces osteolysis, results in a substantial cost savings to the healthcare system, and reduces patient pain and suffering.
  • For a better understanding of the present invention, together with other and further objects thereof, reference is made to the accompanying drawings and detailed description and its scope will be pointed out in the appended claims.
  • BRIEF DESCRIPTION OF THE DRAWINGS
    • Figure 1 is a schematic view of a gas cluster ion beam processing system of the present invention;
    • Figure 2 is an exploded view of a portion of the gas cluster ion beam processing system showing the workpiece holder;
    • Figure 3 is a schematic view of an alternate embodiment of a gas cluster ion beam processing system of the present invention;
    • Figure 4 is an atomic force microscope image showing the surface of a Co-Cr-Mo alloy artificial hip joint ball after conventional polishing and prior to GCIB processing; and
    • Figure 5 is an atomic force microscope image showing the surface of the hip joint ball of Figure 4 after GCIB processing according to a method of the invention.
    DETAILED DESCRIPTION OF THE PREFERRED METHODS AND EMBODIMENTS
  • Beams of energetic ions, electrically charged atoms or molecules accelerated through high voltages under vacuum, are widely utilized to form semiconductor device junctions, to smooth surfaces by sputtering, and to enhance the properties of thin films. Gas cluster ions are formed from large numbers of weakly bound atoms or molecules sharing common electrical charges and accelerated together through high voltages to have high total energies. Cluster ions disintegrate upon impact and the total energy of the cluster is shared among the constituent atoms. Because of this energy sharing, the atoms are individually much less energetic than the case of conventional ions or ions not clustered together and, as a result, the atoms penetrate to much shorter depths. Surface sputtering effects are orders of magnitude stronger than corresponding effects produced by conventional ions, thereby making important microscale surface smoothing effects possible that are not possible in any other way.
  • The concept of gas cluster ion beam (GCIB) processing has only emerged over the past decade. Using a GCIB for dry etching, cleaning, and smoothing of materials is known in the art and has been described, for example, by Deguchi, et al. in U.S. Patent No. 5,814,194 , "Substrate Surface Treatment Method", 1998. Because ionized clusters containing on the order of thousands of gas atoms or molecules may be formed and accelerated to modest energies on the order of a few thousands of electron volts, individual atoms or molecules in the clusters may each only have an average energy on the order of a few electron volts. It is known from the teachings of Yamada in, for example, U.S. Patent 5,459,326 , that such individual atoms are not energetic enough to significantly penetrate a surface to cause the residual sub-surface damage typically associated with plasma polishing. Nevertheless, the clusters themselves are sufficiently energetic (some thousands of electron volts) to effectively etch, smooth, or clean hard surfaces.
  • Because the energies of individual atoms within a gas cluster ion are very small, typically a few eV, the atoms penetrate through only a few atomic layers, at most, of a target surface during impact. This shallow penetration of the impacting atoms means all of the energy carried by the entire cluster ion is consequently dissipated in an extremely small volume in the top surface layer during a period on the order of 10-12 seconds. This is different from the case of ion implantation which is normally done with conventional ions and where the intent is to penetrate into the material, sometimes penetrating several thousand angstroms, to produce changes in the surface properties of the material. Because of the high total energy of the cluster ion and extremely small interaction volume, the deposited energy density at the impact site is far greater than in the case of bombardment by conventional ions.
  • Reference is now made to Figure 1 of the drawings which shows the gas cluster ion beam (GCIB) processor 100 of this invention utilized for the surface smoothing of a surgical implant such as an artificial hip joint component 10. Although not limited to the specific components described herein, the processor 100 is made up of a vacuum vessel 102 which is divided into three communicating chambers, a source chamber 104, an ionization/acceleration chamber 106, and a processing chamber 108 which includes therein a uniquely designed workpiece holder 150 capable of positioning the artificial hip joint for uniform smoothing by a gas cluster ion beam.
  • During the smoothing method of this invention, the three chambers are evacuated to suitable operating pressures by vacuum pumping systems 146a, 146b, and 146c, respectively. A condensable source gas 112 (for example argon, nitrogen, oxygen, or a gas mixture) stored in a cylinder 111 is admitted under pressure through gas metering valve 113 and gas feed tube 114 into stagnation chamber 116 and is ejected into the substantially lower pressure vacuum through a properly shaped nozzle 110, resulting in a supersonic gas jet 118. Cooling, which results from the expansion in the jet, causes a portion of the gas jet 118 to condense into clusters, each consisting of from several to several thousand weakly bound atoms or molecules. A gas skimmer aperture 120 partially separates the gas molecules that have not condensed into a cluster jet from the cluster jet so as to minimize pressure in the downstream regions where such higher pressures would be detrimental (e.g., ionizer 122, high voltage electrodes 126, and process chamber 108). Suitable condensable source gases 112 include, but are not necessarily limited to argon, nitrogen, carbon dioxide, oxygen and mixtures of these gases.
  • After the supersonic gas jet 118 containing gas clusters has been formed, the clusters are ionized in an ionizer 122. The ionizer 122 is typically an electron impact ionizer that produces thermoelectrons from one or more incandescent filaments 124 and accelerates and directs the electrons causing them to collide with the gas clusters in the gas jet 118, where the jet passes through the ionizer 122. The electron impact ejects electrons from the clusters, causing a portion the clusters to become positively ionized. A set of suitably biased high voltage electrodes 126 extracts the cluster ions from the ionizer 122, forming a beam, then accelerates the cluster ions to a desired energy (typically from 1 keV to several tens of keV) and focuses them to form a GCIB 128 having an initial trajectory 154. Filament power supply 136 provides voltage VF to heat the ionizer filament 124. Anode power supply 134 provides voltage VA to accelerate thermoelectrons emitted from filament 124 to cause them to bombard the cluster containing gas jet 118 to produce ions. Extraction power supply 138 provides voltage VE to bias a high voltage electrode to extract ions from the ionizing region of ionizer 122 and to form a GCIB 128. Accelerator power supply 140 provides voltage VAcc to bias a high voltage electrode with respect to the ionizer 122 so as to result in a total GCIB acceleration energy equal to VAcc electron volts (eV). One or more lens power supplies (142 and 144, for example) may be provided to bias high voltage electrodes with potentials (VL1 and VL2 for example) to focus the GCIB 128.
  • A medical device such as an artificial hip joint component 10 (shown in Figure 1 as an acetabular cup, or replaced by a femoral head) to be processed by the GCIB processor 100 is held on a workpiece holder 150, disposed in the path of the GCIB 128 (148). In order for the uniform smoothing of the hip joint component 10 to take place, the workpiece holder 150 is designed in a manner set forth below to appropriately manipulate the hip joint component 10.
  • Referring to Figure 2, it is desirable that the artificial hip joint surfaces that are non-planar, that is may be of a sphere-like or cup-like configuration, preferably remain oriented within a specific angle tolerance with respect to the normal beam incidence to obtain optimal smoothing of the hip joint surfaces utilizing GCIB. It has been determined that optimum smoothing occurs when the GCIB strikes the workpiece at near-normal incidence (for example within +/- 15 degrees of normal), but it has also been shown that incident angles deviating up to about 45° from normal can produce effective smoothing. Additionally in the case of a cup-like joint component, it is necessary that appropriate portions of the interior surface of the cup be processed despite the fact that the rim of the cup may shadow portions of the interior surface in certain orientations. This requires a hip joint fixture or workpiece holder 150 with the ability to be fully articulated to orient all non-planar surfaces to be modified within that angle tolerance at a constant exposure level for process optimization and uniformity. More specifically, when smoothing an artificial hip joint component 10, the workpiece holder 150 is rotated and articulated by a mechanism 152 located at the end of the GCIB processor 100. The articulation/rotation mechanism 152 preferably permits 360 degrees of device rotation about longitudinal axis 154 and sufficient device articulation about an axis 156 perpendicular to axis 154 to preferably maintain the artificial hip joint surface to within +/- 15 degrees from normal beam incidence.
  • Under certain conditions, depending upon the size of the artificial hip joint component 10, a scanning system may be desirable to produce uniform smoothness. Although not necessary for GCIB processing, as shown in Figure 1, two pairs of orthogonally oriented electrostatic scan plates 130 and 132 may be utilized to produce a raster or other scanning pattern over an extended processing area. When such beam scanning is performed, a scan generator 156 provides X-axis and Y-axis scanning signal voltages to the pairs of scan plates 130 and 132 through lead pairs 158 and 160 respectively. The scanning signal voltages are commonly triangular waves of different frequencies that cause the GCIB 128 to be converted into a scanned GCIB 148, which scans the entire surface of the hip joint component 10. Although electrostatic scanning of the GCIB 128 across the workpiece is illustrated, it is also possible (not shown) to achieve similar results by holding the GCIB 128 stationary and mechanically scanning the workpiece through the beam to achieve processing of large workpieces.
  • When beam scanning over an extended region is not desired, processing is generally confined to a region that is defined by the diameter of the beam. The diameter of the beam at the workpiece's surface can be set by selecting the voltages (VL1 and/or VL2) of one or more lens power supplies (142 and 144 shown for example) to provide the desired beam diameter at the workpiece.
  • Figure 3 shows an alternate embodiment gas cluster ion beam processing system 200 of the present invention, similar to the gas cluster ion beam processing system 100 of Figure 1, but having been configured somewhat differently for GCIB processing of sphere-like workpiece 20, for example the ball portion of a hip joint prostheses for surgical implantation. A scanned GCIB 148 is directed toward the sphere-like workpiece 20 disposed in the path of the scanned GCIB 148 in such a way that it intercepts a portion of the scanned GCIB 148. The portion of the scanned GCIB which is not intercepted by the workpiece 20 continues and strikes ion beam current collector 212, which collects electrical current due to the ions in the portion of scanned GCIB 148 that strikes the collector 212. The scanned GCIB 148 scans across a predetermined area on the surface of the current collector 212, the area including the area shadowed by the workpiece 20. The ion current collected by the charge collector 212 flows through electrical lead 214 into current integrator/processor 218, which integrates the collected current and, by taking into account the predetermined fraction of the scanned beam that is intercepted by the workpiece, calculates and displays the total dose, in ions/cm2, that would irradiate the workpiece if it were a flat surface perpendicular to the beam axis 220 and having a circular radius equal to the radius of the sphere-like workpiece 20. Workpiece 20 typically has a opening, which may be tapered, that may be used to attach it to the end of a shaft 204 and it is supported and disposed in the beam path by the shaft 204. The shaft 204 passes through rotary motion vacuum feedthrough 208 in an access plate 216 of the processing chamber 108. A conventional rotary motor 210 rotates shaft 204 and attached workpiece 20 during irradiation of the workpiece 20 by the scanned GCIB 148. The motor speed is chosen to provide a rotation period that is short compared to the processing time so that the GCIB dose is deployed circumferentially uniformly about the processed portion of the sphere-like workpiece 20. Rotary shaft 204 is disposed so that its axis of rotation is at an angle 206 to the axis 220 of scanned GCIB 148. Angle 206 is selected to determine the portion of the sphere-like workpiece that receives irradiation by the GCIB 148. It is preferred that angle 206 be in the range of 20° to 50°. Because the workpiece 20 is sphere-like, the total irradiated area of the workpiece is larger than that which the scanned GCIB would irradiate if the the workpiece were a flat circular surface perpendicular to the beam axis 220 and having a circular radius equal to the radius of the sphere-like workpiece 20. The ratio of areas to the irradiated sphere-like object to that of the flat circle is given by the expression: Area ratio = 2 + 2 sin θ , where θ is the angle 206
    Figure imgb0001
  • Accordingly, in order for the sphere-like workpiece 20 to receive a desired average dose in ions/cm2, the dose applied must be indicated by the current integrator/processor 218 to be larger than the desired dose by the factor of the Area ratio given in Eqn. 1. This assures that the average dose received by the sphere-like workpiece is equal to the desired dose, but the dose is not uniform across the surface of the sphere-like workpiece 20. If greater uniformity of dose is desired on the sphere-like workpiece or if it is desired to achieve a more limited range of GCIB incident angle on the workpiece, a more complex positioning mechanism capable of rotating the sphere about two axes can be used, like that shown in Figure 2.
  • It is possible to improve the surface smoothness on artificial hip joint components 10 or 20 utilizing the present invention. A hip component 10 surface composed of a cobalt-chrome alloy had gross surface micro-roughness before GCIB treatment. The surface roughness measured an average roughness (Ra) of 3.86 angstroms and a root-mean-square roughness (RRMS) of 5.28 angstroms. These irregularities highlight the surface micro-roughness problem at the cellular level where osteolysis begins. A hip joint component 10 surface composed of cobalt-chrome alloy after argon GCIB processing showed the surface micro-roughness has been reduced without any measurable physical or structural change to the integrity of the prosthesis itself. The post-GCIB surface roughness measured an Ra of 2.62 angstroms and an RRMS of 3.34 angstroms. Effective argon gas cluster ion beam doses, using beam energies of from about 2 to about 50 keV, for smoothing cobalt-chrome alloy surfaces are typically in the range of from about 1 X 1015 ions/cm2 to about 1 X 1017 ions/cm2 and can be determined experimentally for other materials.
  • It has been found that in some cases hip joint prosthesis components prepared and polished conventionally are considerably rougher than in the previous examples given. Figure 4 shows an AFM image of a surface of a hip joint component 20 made from an ASTM F1537 wrought Cobalt-Chrome-Molybdenum (Co-Cr-Mo) alloy prepared and polished conventionally. The AFM-measured Ra of this surface is 21.1 angstroms. It was learned that processing this surface with an argon GCIB failed to produce satisfactory reduction in the Ra of the surface, even with extended processing doses. The AFM image, shown in Figure 4, of the surface prior to GCIB processing is quite rough, with large numbers of elevated regions (asperities). The asperities are seen to fall into two size ranges when viewed on the scale of the AFM image, "small" and "larger". Experimentation revealed that the small asperities and other high spacial frequency roughness features were readily removed by GCIB processing using inert argon gas clusters. The size distribution of the asperities is clearly enough demarcated that it is believed the two sizes may arise from different phenomena. In some AFM images (not shown here) the "small" asperities have a linear streaked surface distribution that suggests that they may be some kind of residue or result of the conventional mechanical polishing process. While the "small" asperities are sometimes organized in a linear streak pattern, the "larger" ones appear randomly oriented, generally fewer in number, and somewhat platelet-like in shape.
  • When ASTM F1537 Co-Cr-Mo alloy is heat treated and forged, face centered cubic cobalt transforms into a hexagonal close-packed phase in the form of small platelets. This creates a dispersion hardened material, with the platelets likely harder than the matrix. Conventional mechanical polishing can be expected to leave them exposed above the softer surface, similar to the AFM image in Figure 4 . Being harder, the platelets could be expected to be etched more slowly by the inert argon GCIB processing that successfully removes the "small" asperities and the high frequency roughness components. It was experimentally determined that by GCIB processing with a reactive gas, the "larger" platelet-like asperities could be removed, leaving in their place etched pits in the surface. It is believed that the reactive GCIB processing preferentially etches the "larger" asperities, which may be of the form of micro-grains of metal of a different phase than the matrix. This leaves a micro-pit where the "larger" asperities previously stood above the surface. Subsequent additional inert argon GCIB processing removes any sharp transitions that may otherwise remain near the pits.
  • Figure 5 shows an AFM image of a surface of a hip joint component 20 composed of an ASTM F1537 wrought Cobalt-Chrome-Molybdenum (Co-Cr-Mo) alloy from the same starting sample as that of Figure 4, but processed using a two step GCIB process according to an embodiment of the present invention. In the first step, the surface is exposed to a dose of approximately 3 X 1016 cluster ions/cm2 of clusters formed from a reactive gas, 50% argon mixed with 50% oxygen. In the second step, the surface is exposed to approximately 3 X 1016 cluster ions/cm2 of clusters formed from the inert gas, argon. The average roughness Ra of this surface as measured by AFM is 15.2 angstroms, notably reduced from the 21.1 Ra of the starting material previously shown in Figure 4, with much of the residual roughness due to the presence of the micro-pits. Furthermore, the nature of the surface is transformed from a surface with elevated asperities, conducive wear and conducive to inducing wear in mating surfaces, to a largely smooth upper surface with scattered smooth micro-pits. The increased smoothness of the upper surface and the greater bearing surface is a significantly superior surface for reduced wear and particle generation in surgically implanted prostheses. Comparison of Figures 4 and 5 shows the dramatic surface improvement obtained by applying both reactive and inert GCIB processing to this hip joint component.
  • Although the invention has been described with respect to various embodiments, it should be realized this invention is also capable of a wide variety of further and other embodiments within the scope of the appended claims.

Claims (10)

  1. A method for smoothing the surface materials of a surgical implant by gas cluster ion beam processing to improve a surface thereof, comprising the steps of:
    ejecting pressurized source gas (112) through a nozzle (110) into a vacuum chamber (102) to form a gas jet (118) comprising gas clusters;
    separating un-clustered gas from gas clusters to form a cluster jet comprising gas clusters;
    ionizing at least a portion of the gas clusters in the cluster jet to form a gas cluster ion beam (128) in the vacuum chamber (102);
    accelerating the gas cluster ion beam (128, 148);
    positioning a surface of the surgical implant (20) in the vacuum chamber to receive the gas cluster ion beam (128, 148) for processing;
    irradiating the surface with a predetermined dose of gas cluster ions having a predetermined energy:
    characterized in that the pressurized source gas includes oxygen and argon, and the cluster jet includes clusters of oxygen and argon, and further in that the step of irradiating provides smoothing of surface material of the surgical implant (20).
  2. The method of claim 1, wherein the pressurized source gas (112) includes about 50% oxygen and about 50% argon.
  3. A method as claimed in claim 1, further comprising the steps of:
    ejecting an inert second pressurized source gas (112') through the nozzle (110) into the vacuum chamber (102) to form a second gas jet (118') comprising inert second gas clusters;
    separating un-clustered gas from the inert second gas clusters to form a second cluster jet comprising inert second gas clusters;
    ionizing at least a portion of the inert second gas clusters in the second cluster jet to form an inert second gas cluster ion beam (128', 148') in the vacuum chamber;
    accelerating the second gas cluster ion beam (128', 148');
    directing the inert second gas cluster ion beam (128', 148') onto the surface of the surgical implant (20); and
    irradiating the surface with a second predetermined dose of the inert second gas cluster ions.
  4. A method as claimed in any of claims 1, 2 or 3, further comprising repositioning the surgical implant (20) to process multiple surface areas of the surgical implant (20).
  5. A method as claimed in claim 4, wherein repositioning the surgical implant (20) comprises rotating the surgical implant (20).
  6. A method as claimed in any of claims 4 or 5, wherein the irradiating of multiple surface regions of the surgical implant (20) comprises irradiation with the gas cluster ion beam (128, 148) incident to the surgical implant surface, with an angle of beam incidence substantially normal thereto, preferably wherein the angle of beam incidence is within +/-15 degrees of normal.
  7. A method as claimed in any of claims 1, 2, 3, 4, 5 or 6, wherein the surgical implant (20) comprises a metal component and preferably, wherein the metal comprises cobalt or an alloy of cobalt.
  8. A method as claimed in any of claims 1, 2, 3, 4, 5, 6 or 7, wherein the surgical implant (20) comprises at least one component of an artificial hip joint.
  9. A polished surgical implant component consisting of a matrix that is a cobalt alloy with included regions of a phase that is harder than the matrix;
    characterized in that the polished surface has been smoothed by the method according to claim 1 and is free of elevated harder-phase asperities.
  10. The surgical implant component of claim 9, wherein the cobalt alloy comprises chrome and molybdenum.
EP01952533.6A 2000-07-10 2001-07-09 Improving effectiveness of artificial hip by gcib Expired - Lifetime EP1301652B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US21731300P 2000-07-10 2000-07-10
US217313P 2000-07-10
PCT/US2001/021562 WO2002004696A1 (en) 2000-07-10 2001-07-09 Improving effectiveness of artificial hip by gcib

Publications (3)

Publication Number Publication Date
EP1301652A1 EP1301652A1 (en) 2003-04-16
EP1301652A4 EP1301652A4 (en) 2006-11-08
EP1301652B1 true EP1301652B1 (en) 2013-09-11

Family

ID=22810532

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01952533.6A Expired - Lifetime EP1301652B1 (en) 2000-07-10 2001-07-09 Improving effectiveness of artificial hip by gcib

Country Status (5)

Country Link
US (1) US6491800B2 (en)
EP (1) EP1301652B1 (en)
JP (1) JP4796737B2 (en)
AU (1) AU2001273274A1 (en)
WO (1) WO2002004696A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11918475B2 (en) 2021-03-31 2024-03-05 DePuy Synthes Products, Inc. Modular acetabular surgical implant assembly

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3352842B2 (en) * 1994-09-06 2002-12-03 科学技術振興事業団 Thin film formation method by gas cluster ion beam
WO2002003883A2 (en) * 2000-07-10 2002-01-17 Epion Corporation Improving effectiveness of medical stents by gcib
US6646277B2 (en) * 2000-12-26 2003-11-11 Epion Corporation Charging control and dosimetry system for gas cluster ion beam
EP1392200B1 (en) * 2001-05-09 2011-10-12 Exogenesis Corporation Method for improving the effectiveness of artificial joints by the application of gas cluster ion beam technology
US8889169B2 (en) * 2001-05-11 2014-11-18 Exogenesis Corporation Drug delivery system and method of manufacturing thereof
US7923055B2 (en) 2001-05-11 2011-04-12 Exogenesis Corporation Method of manufacturing a drug delivery system
DE60237813D1 (en) * 2001-05-11 2010-11-11 Epion Corp METHOD FOR IMPROVING THE EFFECTIVENESS OF MEDICAL DEVICES BY MOUNTING MEDICAMENTS ON THE SURFACE
US20100036502A1 (en) * 2008-08-07 2010-02-11 Exogenesis Corporation Medical device for bone implant and method for producing such device
US7666462B2 (en) * 2001-05-11 2010-02-23 Exogenesis Corporation Method of controlling a drug release rate
US7261914B2 (en) * 2003-09-02 2007-08-28 Southwest Research Institute Method and apparatus for forming a nitride layer on a biomedical device
JP2006089844A (en) * 2004-09-27 2006-04-06 Olympus Corp Superprecision polishing method and superprecision polishing device
US20060093753A1 (en) * 2004-10-29 2006-05-04 Nickel Janice H Method of engineering a property of an interface
US7504135B2 (en) * 2005-02-03 2009-03-17 Samsung Electronics Co., Ltd Method of fabricating a manganese diffusion barrier
US7186992B2 (en) * 2005-02-07 2007-03-06 Hewlett-Packard Development Company, L.P. Method of fabricating a polarizing layer on an interface
US8835880B2 (en) * 2006-10-31 2014-09-16 Fei Company Charged particle-beam processing using a cluster source
US20100227523A1 (en) * 2007-09-14 2010-09-09 Exogenesis Corporation Methods for improving the bioactivity characteristics of a surface and objects with surfaces improved thereby
US8377460B2 (en) * 2007-09-14 2013-02-19 Exogenesis Corporation Method for modifying the wettability and/or other biocompatibility characteristics of a surface of a biological material by the application of gas cluster ion beam technology and biological materials made thereby
US9144627B2 (en) 2007-09-14 2015-09-29 Exogenesis Corporation Methods for improving the bioactivity characteristics of a surface and objects with surfaces improved thereby
US9192694B2 (en) 2007-10-03 2015-11-24 Kyocera Medical Corporation Biocompatible and low-abrasion member, and artificial joint using the same and method of producing the same
US20090204213A1 (en) * 2008-02-13 2009-08-13 Depuy Products, Inc. Metallic implants
US8530859B2 (en) * 2008-06-26 2013-09-10 Exogenesis Corporation Method and system for sterilizing objects by the application of gas-cluster ion-beam technology
EP2323708A4 (en) * 2008-08-07 2015-11-18 Exogenesis Corp Drug delivery system and method of munufacturing thereof
EP2405891B1 (en) * 2009-03-11 2019-07-03 Exogenesis Corporation Method for modifying the wettability and/or other biocompatibility characteristics of a surface of a biological material by the application of gas cluster ion beam technology and biological materials made thereby
CN102348430B (en) * 2009-03-11 2017-09-01 艾克索乔纳斯公司 Improve the method for surface bioactive feature and the object with the surface thus improved
EP2567012B1 (en) * 2010-05-05 2015-12-16 Exogenesis Corporation Methods for improving the bioactivity characteristics of a surface and objects with surfaces improved thereby
US10181402B2 (en) 2010-08-23 2019-01-15 Exogenesis Corporation Method and apparatus for neutral beam processing based on gas cluster ion beam technology and articles produced thereby
US9799488B2 (en) * 2010-08-23 2017-10-24 Exogenesis Corporation Method and apparatus for neutral beam processing based on gas cluster ion beam technology
EP2608872B1 (en) 2010-08-23 2019-07-31 Exogenesis Corporation Method and apparatus for neutral beam processing based on gas cluster ion beam technology
US11199769B2 (en) 2010-08-23 2021-12-14 Exogenesis Corporation Method and apparatus for neutral beam processing based on gas cluster ion beam technology
US10825685B2 (en) 2010-08-23 2020-11-03 Exogenesis Corporation Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby
US10670960B2 (en) 2010-08-23 2020-06-02 Exogenesis Corporation Enhanced high aspect ratio etch performance using accelerated neutral beams derived from gas-cluster ion beams
US20170303383A1 (en) * 2010-08-23 2017-10-19 Exogenesis Corporation Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby
US10202684B2 (en) 2010-08-23 2019-02-12 Exogenesis Corporation Method for neutral beam processing based on gas cluster ion beam technology and articles produced thereby
US10556042B2 (en) 2011-08-19 2020-02-11 Exogenesis Corporation Drug delivery system and method of manufacturing thereof
JP2014525817A (en) 2011-08-22 2014-10-02 エクソジェネシス コーポレーション Method for improving bioactive characteristics of an object surface and surface improved thereby
CA2845762C (en) 2011-08-22 2019-01-08 Exogenesis Corporation Drug delivery system and method of manufacturing thereof
US9114195B2 (en) 2011-08-22 2015-08-25 Exogenesis Corporation Method for modifying the wettability and other biocompatibility characteristics of a surface of a biological material by the application of beam technology and biological materials made thereby
JP5924094B2 (en) 2012-04-18 2016-05-25 新明和工業株式会社 CUTTER, MANUFACTURING METHOD THEREOF, AND PLASMA DEVICE FOR MANUFACTURING THE SAME
KR102257901B1 (en) * 2014-09-19 2021-05-31 삼성전자주식회사 Semiconductor inspection system and a method of inspecing a semiconductor device using the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5459326A (en) * 1991-05-31 1995-10-17 Research Development Corporation Of Japan Method for surface treatment with extra-low-speed ion beam

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4278493A (en) * 1980-04-28 1981-07-14 International Business Machines Corporation Method for cleaning surfaces by ion milling
JPH0639707B2 (en) * 1987-05-15 1994-05-25 日新電機株式会社 Thin film forming equipment
US4968006A (en) * 1989-07-21 1990-11-06 Spire Corporation Ion implantation of spherical surfaces
US5123924A (en) * 1990-04-25 1992-06-23 Spire Corporation Surgical implants and method
US5133757A (en) * 1990-07-31 1992-07-28 Spire Corporation Ion implantation of plastic orthopaedic implants
JPH0698903A (en) * 1992-09-21 1994-04-12 Mitsubishi Materials Corp Production of bioimplant material
JPH07275276A (en) * 1994-04-06 1995-10-24 Nikon Corp Intraosseous implant
JPH07178127A (en) * 1993-12-22 1995-07-18 Mitsubishi Materials Corp Artificial bone
JP3752259B2 (en) * 1994-10-07 2006-03-08 独立行政法人科学技術振興機構 Cluster ion beam sputtering method
US5814194A (en) * 1994-10-20 1998-09-29 Matsushita Electric Industrial Co., Ltd Substrate surface treatment method
JP3451140B2 (en) * 1994-10-26 2003-09-29 科学技術振興事業団 Ultra-precision polishing method using gas cluster ion beam
JPH08283706A (en) * 1995-04-14 1996-10-29 Futaba Corp Method of surface cleaning
JPH0940441A (en) * 1995-07-26 1997-02-10 Canon Inc Aspherical lens processing apparatus and processing method
US5980974A (en) 1996-01-19 1999-11-09 Implant Sciences Corporation Coated orthopaedic implant components
DE19646891A1 (en) * 1996-11-13 1998-05-14 Kubein Meesenburg Dietmar Artificial joint, especially an endoprosthesis to replace natural joints
JPH1179759A (en) * 1997-09-04 1999-03-23 Canon Inc Manufacturing method of optical element molding die

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5459326A (en) * 1991-05-31 1995-10-17 Research Development Corporation Of Japan Method for surface treatment with extra-low-speed ion beam

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11918475B2 (en) 2021-03-31 2024-03-05 DePuy Synthes Products, Inc. Modular acetabular surgical implant assembly

Also Published As

Publication number Publication date
WO2002004696A1 (en) 2002-01-17
AU2001273274A1 (en) 2002-01-21
EP1301652A4 (en) 2006-11-08
US6491800B2 (en) 2002-12-10
US20020017455A1 (en) 2002-02-14
EP1301652A1 (en) 2003-04-16
JP2004502514A (en) 2004-01-29
JP4796737B2 (en) 2011-10-19

Similar Documents

Publication Publication Date Title
EP1301652B1 (en) Improving effectiveness of artificial hip by gcib
EP1392200B1 (en) Method for improving the effectiveness of artificial joints by the application of gas cluster ion beam technology
US7105199B2 (en) Methods of adhering drugs to the surface of medical devices through ion beam surface modification
US9226998B2 (en) Method of manufacturing a drug delivery system using gas cluster ion beam irradiation
US6676989B2 (en) Method and system for improving the effectiveness of medical stents by the application of gas cluster ion beam technology
US8187662B2 (en) Method of controlling a drug release rate
US5603338A (en) Implant surface preparation utilizing acid treatment
US20020017454A1 (en) Method and system for improving the effectiveness of intraocular lenses by the application of gas cluster ion beam technology
US20090198264A1 (en) Method and System for Improving Surgical Blades by the Application of Gas Cluster Ion Beam Technology and Improved Surgical Blades
KR101181449B1 (en) Method of improving wear resistance of polymeric material for artificial joint and apparatus thereof
EP2747711B1 (en) Medical device for bone implant and method for producing such a device
EP2567012A1 (en) Methods for improving the bioactivity characteristics of a surface and objects with surfaces improved thereby
US20180321583A1 (en) Medical device for bone implant and method for producing such a device

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030210

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB

A4 Supplementary search report drawn up and despatched

Effective date: 20061006

17Q First examination report despatched

Effective date: 20070319

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TEL EPION INC.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EXOGENESIS CORPORATION

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EXOGENESIS CORPORATION

RIC1 Information provided on ipc code assigned before grant

Ipc: A61F 2/30 20060101ALI20120703BHEP

Ipc: C23C 14/48 20060101AFI20120703BHEP

Ipc: C23C 14/50 20060101ALI20120703BHEP

Ipc: H01J 37/317 20060101ALI20120703BHEP

Ipc: C23F 1/04 20060101ALI20120703BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIN1 Information on inventor provided before grant (corrected)

Inventor name: DIFILIPPO, VINCENT, C/O EXOGENESIS CORPORATION

Inventor name: KIRKPATRICK, ALLEN, R., C/O EXOGENESIS CORPORATION

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EXOGENESIS CORPORATION

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130626

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60148316

Country of ref document: DE

Effective date: 20131031

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60148316

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20140612

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60148316

Country of ref document: DE

Effective date: 20140612

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190725

Year of fee payment: 19

Ref country code: DE

Payment date: 20190729

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190729

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60148316

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200709

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210202